Cationically modified, anionic polyurethane dispersions

ABSTRACT

The invention describes cationically modified particulate anionic polyurethanes having a particle size from 10 nm to 10 μm, the particulate polyurethanes being cationically modified through surface coating with cationic polymers. Preferred cationic polymers are polymers containing vinylamine units, polymers containing vinylimidazole units, polymers containing quaternary vinylimidazole units, condensates of imidazole and epichlorohydrin, crosslinked polyamidoamines, ethyleneimine-grafted crosslinked polyamidoamines, polyethyleneimines, alkoxylated polyethyleneimines, crosslinked polyethyleneimines, amidated polyethyleneimines, alkylated polyethyleneimines, polyamines, amine-epichlorohydrin polycondensates, alkoxylated polyamines, polyallylamines, polydimethyldiallylammonium chlorides, polymers containing basic (meth)acrylamide or (meth)acrylic ester units, polymers containing basic quaternary (meth)acrylamide or (meth)acrylic ester units, and/or lysine condensates.

The present invention relates to cationically modified particulateanionic polyurethanes, aqueous polyurethane dispersions containing same,the use of the particulate polyurethanes and of the polyurethanedispersions, processes for treating surfaces and treatment compositionstherefor which contain the cationically modified particulate anionicpolyurethanes.

Anionic polyurethane dispersions are used in industry for modifying theproperties of surfaces. For example, aqueous anionic polyurethanedispersions are used in concentrated form for finishing and coatingtextiles and textile substrates and in leather finishing. Thedispersions are applied to a substrate by common methods, for exampleknifecoating, brushing, saturating or impregnating, and then dried. Inthe process, the finely divided particles form a film and confer novelproperties on the surface to which they have been applied.

Washing, rinsing, cleaning and conditioning operations are by contrastcustomarily carried out in a very dilute aqueous liquor, and theingredients of the particular formulation employed do not remain on thesubstrate, but instead are disposed of with the wastewater. Modificationof surfaces with anionic polyurethane dispersions from a dilute aqueousliquor is achieved only to an entirely unsatisfactory degree owing tothe insufficient surface affinity of the polyurethane particles.

U.S. Pat. No. 3,580,853 describes a detergent composition containingwater-insoluble particulate substances such as biocides and certaincationic polymers which serve to enhance the deposition and retention ofthe biocides on surfaces washed with the detergent composition.

U.S. Pat. No. 5,476,660 discloses using polymeric retention aids forcationic or zwitterionic dispersions of polystyrene or wax which containan active substance embedded in the dispersed particles. These dispersedparticles are referred to as “carrier particles” because they adhere tothe treated surface, where they release the active substance, forexample when used in surfactant-containing formulations.

WO 01/94516 describes the use of cationically modified particulatehydrophobic polymers based on ethylenically unsaturated monomers inrinsing or conditioning compositions for textiles and in laundrydetergents. The particulate hydrophobic polymers are preferablyconstructed of water-insoluble nonionic monomers such as alkylacrylates. The cationic modification is effected by coating thehydrophobic polymer particles with cationic polymers.

WO 01/94517 describes the use of cationically modified particulatehydrophobic polymers based on ethylenically unsaturated monomers inrinsing, cleaning and impregnating compositions for hard surfaces.

It is an object of the present invention to provide treatmentcompositions for textile and nontextile materials that can be used evenin a very dilute aqueous liquor and that confer advantageous propertieson the surfaces of the treated materials or the materials themselves.

We have found that this object is achieved by cationically modifiedparticulate anionic polyurethanes having a particle size from 10 nm to10 μm, the particulate polyurethanes being cationically modified throughsurface coating with cationic polymers, and also by cationicallymodified aqueous anionic polyurethane dispersions which include saidcationically modified particulate anionic polyurethanes.

The present invention further provides for the use of the cationicallymodified particulate anionic polyurethanes as a surface-modifyingadditive in washing, rinsing, conditioning or cleaning compositions.

The present invention further provides for the use of the cationicallymodified aqueous anionic polyurethane dispersions as a rinsing, washingor cleaning liquor.

The particulate polyurethanes which are cationically modified throughsurface coating contain anionic groups. They may additionally containcationic groups as well, provided the particles have a net anioniccharge overall. The net anionic charge causes the polyurethane particlesto migrate to the anode in an electric field at a given pH. Thus, notonly purely anionic but also amphoteric polyurethane dispersions can becationically modified, as long as the anionc character of thepolyurethane dispersions predominates, ie the molar fraction of theanionic units in the polymer is larger than the molar fraction of thecationic units in the polymer. Such polyurethane dispersions ofpredominantly anionic character are hereinafter referred to as anionicpolyurethane dispersions. Coating the particle surface of the anionicpolyurethane particles with cationic polymers renders these anionicpolyurethane particles cationic, so that the particles have a netcationic charge on the surface and their direction of migration in anelectric field reverses.

The cationically surface-modified particulate polyurethanes areobtainable for example by treatment of aqueous anionic polyurethanedispersions comprising polyurethane particles from 10 mm to 10 μm insize with an aqueous solution or dispersion of a cationic polymer. Thisis accomplished most simply by combining the aqueous anionicpolyurethane dispersion which contains particles from 10 nm to 10 μm inparticle size with the aqueous solution or dispersion of the cationicpolymer. The cationic polymers are preferably used in the form ofaqueous solutions. However, it is also possible to use aqueousdispersions of cationic polymers, in which case the cationic polymerparticles dispersed therein have an average diameter of up to 1 μm.

The mixing of the aqueous anionic polyurethane dispersion and of thesolution or dispersion of the cationic polymers can be effected at forexample 0-100° C. The amount of cationic polymers which is needed toeffect cationic modification is dependent not only on the net surfacecharge of the polyurethane particles but also on the charge density ofthe cationic polymers at the pH prevailing during the coating of thepolyurethane particles with the cationic polymers. The weight ratio ofdispersed polyurethane particles to cationic polymers is generally inthe range from 100:0.5 to 100:5.

Surprisingly, the presence of the cationic polymers does not induce acoagulation of the oppositely charged anionic dispersion particles,rather the dispersions of the cationically modified particles obtainedare stable.

Cationic modification enhances the affinity of the anionic polyurethaneparticles for the surface to be treated, for example the surface of atextile fiber, to such an extent that the polyurethane particles willreadily absorb onto the surface from very dilute aqueous treatmentliquors, while it preserves the desirable film-forming,surface-modifying properties of the anionic polyurethane particles.

A Aqueous Polyurethane Dispersions

The aqueous anionic polyurethane dispersions are conveniently preparedby reacting

-   -   a) polyisocyanates having from 4 to 30 carbon atoms,    -   b) diols of which    -   b1) from 10 to 100 mol %, based on total diols (b), have a        molecular weight from 500 to 5000, and        -   b2) from 0 to 90 mol %, based on total diols (b), have a            molecular weight from 62 to 500 g/mol,    -   c) optionally further polyfunctional compounds, other than said        diols (b), having reactive groups selected from alcoholic        hydroxyl groups and primary or secondary amino groups, and    -   d) monomers, other than said monomers (a), (b) and (c), which        bear at least one isocyanate group or at least one        isocyanate-reactive group and which in addition bear at least        one hydrophilic group I or a potentially hydrophilic group        whereby the polyurethanes are rendered dispersible in water,        to form a polyurethane.

Useful monomers (a) include the polyisocyanates customarily used inpolyurethane chemistry.

Of particular interest are diisocyanates X(NCO)₂, where X is aliphatichydrocarbyl having from 4 to 12 carbon atoms, cycloaliphatic or aromatichydrocarbyl having from 6 to 15 carbon atoms or araliphatic hydrocarbylhaving from 7 to 15 carbon atoms. Examples of such diisocyanates aretetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylenediisocyanate, 1,4-diisocyanatocycohexane,1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI),2,2-bis-(4-isocyanatocyclohexyl)-propane, trimethylhexane diisocyanate,1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene,2,6-diisocyanatotoluene, 4,4′-diisocyanatodiphenylmethane,2,4-diisocyantodiphenylmethane, p-xylylene diisocyanate, m- andp-α,α,α′,α′-tetramethylxylylene diisocyanate (TMXDI), the isomers ofbis-(4-isocyanatocyclohexyl)methane such as the trans/trans, the cis/cisand the cis/trans isomers, and also mixtures thereof.

Useful mixtures of these isocyanates include particularly the mixturesof the respective structural isomers of diisocyanatotoluene anddiisocyanatodiphenylmethane, especially the mixture of 20 mol % of2,4-diisocyanatotoluene and 80 mol % of 2,6-diisocyanatotoluene.Furthermore, the mixtures of aromatic isocyanates such as2,4-diisocyanatotoluene and/or 2,6-diisocyanatotoluene with aliphatic orcycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDIare particularly advantageous, the preferred mixing ratio of aliphaticto aromatic isocyanates being in the range from 4:1 to 1:4.

As compounds (a) it is further possible to use isocyanates which, aswell as free isocyanate groups, bear capped isocyanate groups, forexample uretidione or urethane groups.

It is optionally possible to use in addition isocyanates having only oneisocyanate group. Generally, their fraction is not more than 10 mol %,based on total monomers. The monoisocyanates customarily bear furtherfunctional groups such as olefinic groups or carbonyl groups and serveto introduce into the polyurethane functional groups effective to permitdispersion or crosslinking or further polymer-analogous reaction of thepolyurethane. Monoisocyanates contemplated for the purpose includemonomers such as isopropenyl α,α-dimethylbenzylisocyanate (TMI).

To prepare polyurethanes having a certain degree of branching orcrosslinking, it is possible to use for example trifunctional ortetrafunctional isocyanates. Isocyanates of this type are obtained forexample on reacting difunctional isocyanates with each other byderivatizing some of their isocyanate groups to allophanate orisocyanurate groups. Commercially available compounds include forexample the isocyanurate of hexamethylene diisocyanate.

With regard to good filming and elasticity, useful diols (b) includeprimarily comparatively high molecular diols (b1) having a molecularweight of about 500-5000 and preferably of about 1000-3000 g/mol.

The diols (b1) are especially polyesterpolyols, which are known forexample from Ullmanns Enzyklopädie der technischen Chemie, 4th edition,Volume 19, pages 62 to 65. Preference is given to using polyesterpolyolswhich are obtained by reaction of dihydric alcohols with dibasiccarboxylic acids. Instead of the free polycarboxylic acids it is alsopossible to use the corresponding polycarboxylic anhydrides orcorresponding polycarboxylic esters of lower alcohols or mixturesthereof for preparing the polyesterpolyols. The polycarboxylic acids canbe aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic andcan be unsaturated and/or substituted, for example by halogen atoms.Examples are suberic acid, azelaic acid, phthalic acid, isophthalicacid, phthalic anhydride, tetrahydrophthalic anhydride,hexahydrophthalic anhydride, tetrachlorophthalic anhydride,endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleicacid, maleic anhydride, fumaric acid, dimeric fatty acids. Preference isgiven to dicarboxylic acids of the general formula HOOC—(CH₂)_(y)—COOH,where y is from 1 to 20, preferably an even number from 2 to 20, e.g.,succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid.

Suitable polyhydric alcohols include, for example, ethylene glycol,1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butenediol,1,4-butynediol, 1,5-pentanediol, neopentylglycol,bis(hydroxymethyl)cyclohexanes such as1,4-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1,3-diol, alsodiethylene glycol, triethylene glycol, tetraethylene glycol,polyethylene glycol, dipropylene glycol, polypropylene glycol,dibutylene glycol and polybutylene glycols. Preference is given toalcohols of the general formula HO—(CH2)_(x)—OH, where x is from 1 to20, preferably an even number from 2 to 20. Examples thereof areethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and1,12-dodecanediol.

Also suitable are polycarbonatediols as are obtainable, for example, byreaction of phosgene with an excess of the low molecular weight alcoholsmentioned as formative components for the polyesterpolyols.

It is also possible to use lactone-based polyesterdiols, ie, homo- orcopolymers of lactones, preferably terminal hydroxyl-functional additionproducts of lactones on suitable difunctional initiator molecules.Preferred lactones are derived from hydroxycarboxylic acids, of thegeneral formula HO—(CH₂)_(z)—COOH, where z is from 1 to 20, preferablyan odd number from 3 to 19, e.g. ε-caprolactone, β-propiolactone,γ-butyrolactone and/or methyl-ε-caprolactone and also mixtures thereof.Suitable initiator components include, for example, the low molecularweight dihydric alcohols mentioned above as formative components for thepolyesterpolyols. The corresponding addition polymers of ε-caprolactoneare particularly preferred. Similarly, lower polyesterdiols orpolyetherdiols can be used as initiators for preparing the lactoneaddition polymers. Instead of the addition polymers of lactones it isalso possible to use the corresponding, chemically equivalentpolycondensates of the hydroxycarboxylic acids corresponding to thelactones.

Useful monomers (b1) further include polyetherdiols. They are obtainablein particular by homopolymerization of ethylene oxide, propylene oxide,butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, forexample in the presence of BF₃, or by the addition of these compounds,optionally mixed or in succession, to initiating components havingreactive hydrogen atoms, such as alcohols or amines, e.g., water,ethylene glycol, 1,2-propanediol, 1,3-propanediol,2,2-bis(4-hydroxydiphenyl)propane or aniline. Particular preference isgiven to polytetrahydrofuran having a molecular weight of from 2 000 to5000, especially from 3 500 to 4500.

The polyesterdiols and polyetherdiols may be used as mixtures in a ratioin the range from 0.1:1 to 9:1.

The hardness and the modulus of elasticity of the polyurethanes can beincreased by using as diols (b) not only diols (b1) but additionally lowmolecular weight diols (b2) having a molecular weight of from about 50to 500, preferably from 60 to 200, g/mol.

Useful monomers (b2) include especially the formative components for theshort chain alkanediols mentioned for preparing polyesterpolyols,preference being given to the unbranched diols having from 2 to 12carbon atoms and an even number of carbon atoms and also to1,5-pentanediol and neopentylglycol.

The proportion of diols (b1), based on total diols (b), is preferablyfrom 10 to 100 mol % and the proportion of monomers (b2), based on totaldiols (b), is preferably from 0 to 90 mol %. The ratio of diols (b1) tomonomers (b2) is particularly preferably within the range from 0.2:1 to5:1, particularly preferably within the range from 0.5:1 to 2:1.

The monomers (c), which differ from the diols (b), generally serve thepurpose of crosslinking or of chain extension. They are generally morethan dihydric nonaromatic alcohols, amines having 2 or more primaryand/or secondary amino groups and also compounds which bear one or moreprimary and/or secondary amino groups alongside one or more alcoholichydroxyl groups.

Alcohols having a hydricness higher than 2, which can be used to set acertain degree of branching or crosslinking, are, for example,trimethylolpropane, glycerol or sugars.

It is also possible to use monoalcohols which, as well as the hydroxylgroup, bear a further isocyanate-reactive group such as monoalcoholshaving one or more primary and/or secondary amino groups, e.g.,monoethanolamine.

Polyamines having 2 or more primary and/or secondary amino groups areused in particular when the chain extension or crosslinking is to takeplace in the presence of water, since amines generally react faster withisocyanates than alcohols or water. This is frequently necessary whenaqueous dispersions of crosslinked polyurethanes or polyurethanes havinga high molecular weight are desired. In such cases, prepolymers withisocyanate groups are prepared, rapidly dispersed in water andsubsequently chain extended or crosslinked by addition of compoundshaving a plurality of isocyanate-reactive amino groups.

Suitable amines for this purpose are generally polyfunctional amines ofthe molecular weight range from 32 to 500 g/mol, preferably from 60 to300 g/mol, which contain at least two amino groups selected from thegroup of the primary and secondary amino groups. Examples thereof arediamines such as diaminoethane, diaminopropanes, diaminobutanes,diaminohexanes, piperazine, 2,5-dimethylpiperazine,amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine,IPDA), 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane,aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines suchas diethylenetriamine or 1,8-diamino-4-aminomethyloctane.

The amines can also be used in blocked form, for example in the form ofthe corresponding ketimines (see for example CA-1 129 128), ketazines(cf. for example U.S. Pat. No. 4,269,7 48) or amine salts (see U.S. Pat.No. 4,292,226). Similarly, oxazolidines as used in U.S. Pat. No.4,192,937, for example, are capped polyamines which can be used to chainextend the prepolymers in the preparation of the polyurethanes of thepresent invention. When such capped polyamines are used, they aregenerally mixed with the prepolymers in the absence of water and thismixture is subsequently mixed with the dispersion water or a portion ofthe dispersion water, so that the corresponding polyamines are releasedhydrolytically.

Preference is given to using mixtures of di- and triamines, particularlypreferably mixtures of isophoronediamine and diethylenetriamine.

The polyurethanes preferably contain no polyamine or from 1 to 10,particularly preferably from 4 to 8, mol %, based on the total amount ofcomponents (b) and (c), of a polyamine having at least 2isocyanate-reactive amino groups as monomer (c).

It is further possible to use, for chain termination, minor amounts, iepreferably amounts of less than 10 mol %, based on the components (b)and (c), of monoalcohols. Their function is generally similar to that ofthe monoisocyanates, ie they mainly serve to functionalize thepolyurethane. Examples are esters of acrylic or methacrylic acid such ashydroxyethyl acrylate or hydroxyethyl methacrylate.

To render the polyurethanes water dispersible, they are polymerized notonly from the components (a), (b) and (c) but also monomers (d) whichdiffer from components (a), (b) and (c) and which bear one or moreisocyanate or isocyanate-reactive groups and additionally at least onehydrophilic group or a group which is convertible into a hydrophilicgroup. In what follows, the expression “hydrophilic groups orpotentially hydrophilic groups” is abbreviated to “(potentially)hydrophilic groups”. The (potentially) hydrophilic groups reactsignificantly more slowly with isocyanates than the functional groups ofthe monomers which serve to polymerize the polymer backbone. The(potentially) hydrophilic groups may be nonionic or preferably ionichydrophilic groups or potentially ionic hydrophilic groups.

The proportion of the total amount of components (a), (b), (c) and (d)which is attributable to components having (potentially) hydrophilicgroups is generally determined so that the molar amount of the(potentially) hydrophilic groups is from 30 to 1000, preferably from 50to 500, particularly preferably from 80 to 300, mmol/kg, based on theweight of all monomers (a) to (b).

Suitable nonionic hydrophilic groups include in particular polyethyleneglycol ethers containing preferably from 5 to 100, preferably from 10 to80, ethylene oxide repeat units. >The level of polyethylene oxide unitsis generally within the range from 0 to 10, preferably from 0 to 6,% byweight, based on the weight of all monomers (a) to (d).

Preferred monomers with nonionic hydrophilic groups are polyethyleneglycol and diisocyanates which bear a terminally etherified polyethyleneglycol radical. Such diisocyanates and methods for their preparation aredescribed in U.S. Pat. Nos. 3,905,929 and 3,920,598.

Ionic hydrophilic groups include in particular anionic groups such asthe sulfonate, the carboxylate and the phosphate group in the form oftheir alkali metal or ammonium salts and also cationic groups such asammonium groups, especially protonated tertiary amino groups orquaternary ammonium groups.

Potentially ionic hydrophilic groups are in particular those which canbe converted by simple neutralization, hydrolysis or quaternizationreactions into the abovementioned ionic hydrophilic groups, e.g.,carboxylic acid groups, anhydride groups or tertiary amino groups.

(Potentially) ionic monomers (d) are extensively described for examplein Ullmanns Enzyklopädie der technischen Chemie, 4th edition, Volume 19,pages 311-313, and, for example, in DE-A 1 495 745.

Potentially cationic monomers (d) of particular practical importance arein particular monomers having tertiary amino groups, for exampletris(hydroxyalkyl)amines, N,N′-bis(hydroxyalkyl)alkylamines,N-hydroxyalkyldialkylamines, tris-(aminoalkyl)amines,N,N′-bis(aminoalkyl)alkylamines, N-aminoalkyldialkylamines, the alkylradicals and alkanediyl units of these tertiary amines containing from 2to 6 carbon atoms independently of each other. Also suitable arepolyethers having tertiary nitrogen atoms and preferably two terminalhydroxyl groups, as are obtainable in a conventional manner, forexample, by alkoxylation of amines having two hydrogen atoms attached toamine nitrogen, e.g., methylamine, aniline or N,N′-dimethylhydrazine.Such polyethers generally have a molecular weight within the range from500 to 6000 g/mol.

These tertiary amines are converted into the ammonium salts either withacids, preferably strong mineral acids such as phosphoric acid, sulfuricacid, or halohydric acids, or by reaction with suitable quaternizingagents such as C₁-C₆-alkyl halides, for example bromides or chlorides.

Suitable monomers with potentially anionic groups customarily includealiphatic, cycloaliphatic, araliphatic or aromatic mono- anddihydroxycarboxylic acids which bear at least one alcoholic hydroxylgroup or at least one primary or secondary amino group. Preference isgiven to dihydroxyalkylcarboxylic acids, especially having from 3 to 10carbon atoms, as also described in U.S. Pat. No. 3,412,054. Particularpreference is given to compounds of the general formula

where R¹ and R² are each a C₁-C₄-alkanediyl unit and R³ is a C₁-C₄-alkylunit, and especially dimethylolpropionic acid (DMPA).

Also suitable are the corresponding dihydroxysulfonic acids anddihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid.

It is also possible to use dihydroxy compounds having a molecular weightof from above 500 to 10,000 g/mol and at least 2 carboxylate groups,known from DE-A 4 140 486. They are obtainable by reaction of dihydroxycompounds with tetracarboxylic dianhydrides such as pyromelliticdianhydride or cyclopentanetetracarboxylic dianhydride in a molar ratioof from 2:1 to 1.05:1 in a polyaddition reaction. Suitable dihydroxycompounds are in particular the monomers (b2) cited as chain extendersand also the diols (b1).

Suitable monomers (d) with isocyanate-reactive amino groups are aminoacids such as lysine, β-alanine, the adducts, mentioned in DE-A-20 34479, of aliphatic diprimary diamines with α,β-unsaturated carboxylic orsulfonic acids. Such compounds conform for example to the formula IH₂N—R—NH—R′—X   (I)where R and R′ are independently a C₁-C₆-alkanediyl unit, preferablyethylene, and X is COOH or SO₃H. Particularly preferred compounds of theformula I are N-(2-aminoethyl)-2-aminoethanecarboxylic acid andN-(2-aminoethyl)-2-aminoethanesulfonic acid and the corresponding alkalimetal salts, sodium being particularly preferred as counterion.

If monomers having potentially ionic groups are used, their conversioninto the ionic form can take place before, during, but preferably afterthe isocyanate polyaddition reaction, since ionic monomers arefrequently only sparingly soluble in the reaction mixture. Thecarboxylate groups are particularly preferably present in the form oftheir salts with an alkali metal ion or an ammonium ion as counterion.

The monomers (d) and their proportions are chosen so as to confer a netanionic character on the polyurethane dispersions obtained.

In the field of polyurethane chemistry it is common knowledge how themolecular weight of the polyurethanes can be set via the choice of theproportions of the mutually reactive monomers and via the arithmeticmean of the number of reactive functional groups per molecule.

The components (a), (b), (c) and (d) and also their respective molarquantities are normally chosen so that the ratio A:B where

-   -   A) is the molar quantity of isocyanate groups and    -   B) is the sum total of the molar quantity of hydroxyl groups and        the molar quantity of functional groups capable of reacting with        isocyanates in an addition reaction        is within the range from 0.5:1 to 2:1, preferably within the        range from 0.8:1 to 1.5, particularly preferably within the        range from 0.9:1 to 1.2:1. The ratio of A:B is most preferably        very close to 1:1.

As well as the components (a), (b), (c) and (d), monomers having justone reactive group are generally used in amounts of up to 15 mol % andpreferably up to 8 mol %, based on the total amount of the components(a), (b), (c) and (d).

The polyaddition of the components (a) to (d) is generally effected atreaction temperatures from 20 to 180° C. and preferably from 50 to 150°C. under atmospheric pressure.

The requisite reaction times can range from a few minutes to severalhours. In the field of polyurethane chemistry it is known how thereaction time is affected by a multiplicity of parameters such astemperature, concentration of the monomers, reactivity of the monomers.

The reaction of the diisocyanates can be catalyzed using customarycatalysts, such as dibutyltin dilaurate, tin(II) octoate ordiazabicyclo[2.2.2]octane.

A suitable apparatus for carrying out the polymerization is a stirredtank, especially when solvents are used to ensure a low viscosity andgood heat removal.

If the reaction is carried out with a solvent, the usually highviscosities and the usually only short reaction times mean thattypically extruders are suitable, especially selfcleaning multiscrewextruders.

The dispersions are usually prepared by one of the following processes:

In the acetone process, an anionic polyurethane is prepared fromcomponents (a) to (d) in a water-miscible solvent having an atmosphericpressure boiling point of below 100° C. Sufficient water is added toform a dispersion in which water is the coherent phase.

The prepolymer blending process differs from the acetone process in thatthe initial product is not a fully reacted (potentially) anionicpolyurethane but a prepolymer which bears isocyanate groups. Thecomponents (a) to (d) here are chosen so that the defined A:B ratio iswithin the range from greater than 1.0 to 3, preferably within the rangefrom 1.05 to 1.5. The prepolymer is first dispersed in water and thencrosslinked by reaction of the isocyanate groups with amines bearingmore than 2 isocyanate-reactive amino groups or chain extended withamines bearing 2 isocyanate-reactive amino groups. Chain extension takesplace even when no amine is added. In this case, isocyanate groups arehydrolyzed to amino groups which react with any remaining isocyanategroups of the prepolymers to effect chain extension.

If a solvent was used in the synthesis of the polyurethane, most of itis typically removed from the dispersion, for example by distillationunder reduced pressure. The dispersions preferably have a solventcontent of less than 10% by weight and are particularly preferably freefrom solvent.

The dispersions generally have a solids content from 10 to 75,preferably from 20 to 65,% by weight and a viscosity of from 10 to 500mPas (measured at 20° C. and a shear rate of 250 s⁻¹).

B Cationic Polymers

Useful cationic polymers for modifying the aqueous anionic polyurethanedispersions include all natural or synthetic cationic polymers whichcontain amino and/or ammonium groups and are soluble in water. Examplesof such cationic polymers are polymers containing vinylamine units,polymers containing vinylimidazole units, polymers containing quaternaryvinylimidazole units, condensates of imidazole and epichlorohydrin,crosslinked polyamidoamines, ethyleneimine-grafted crosslinkedpolyamidoamines, polyethyleneimines, alkoxylated polyethyleneimines,crosslinked polyethyleneimines, amidated polyethyleneimines, alkylatedpolyethyleneimines, polyamines, amine-epichlorohydrin polycondensates,alkoxylated polyamines, polyallylamines, polydimethyldiallylammoniumchlorides, polymers containing basic (meth)acrylamide or (meth)acrylicester units, polymers containing basic quaternary (meth)acrylamide or(meth)acrylic ester units, and/or lysine condensates.

Cationic polymers also include amphoteric polymers having a net cationiccharge, ie, the polymers contain anionic as well as cationic monomers incopolymerized form, but the molar fraction of the cationic units presentin the polymer is larger than that of the anionic units.

Polymers containing vinylamine units are prepared for example fromopen-chained N-vinylcarboxamides of the formula (I)

where R¹ and R², which may be identical or different, are each selectedfrom the group consisting of hydrogen and C₁-C₆-alkyl. Useful monomersinclude for example N-vinylformamide (R¹═R²═H in formula I),N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide,N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide andN-vinylpropionamide. The monomers mentioned may be polymerized eitheralone or mixed with each other or together with other monoethylenicallyunsaturated monomers to prepare the polymers. Preference is given tostarting from homo- or copolymers of N-vinylformamide. Polymerscontaining vinylamine units are known for example from U.S. Pat. No.4,421,602, EP-A-0 216 387 and EP-A-0 251 182. They are obtained byhydrolysis, with acids, bases or enzymes, of polymers containingmonomers of the formula (I) in polymerized form.

Useful monoethylenically unsaturated monomers for copolymerization withN-vinylcarboxamides include all compounds that are copolymerizabletherewith. Examples thereof are vinyl esters of saturated carboxylicacids of from 1 to 6 carbon atoms such as vinyl formate, vinyl acetate,vinyl propionate and vinyl butyrate and vinyl ethers such as C₁-C₆-alkylvinyl ethers, for example methyl vinyl ether or ethyl vinyl ether.Useful comonomers further include ethylenically unsaturatedC₃-C₆-carboxylic acids, for example acrylic acid, methacrylic acid,maleic acid, crotonic acid, itaconic acid and vinylacetic acid and alsotheir alkali metal and alkaline earth metal salts, esters, amides andnitriles of the carboxylic acids mentioned, for example methyl acrylate,methyl methacrylate, ethyl acrylate and ethyl methacrylate.

Useful monoethylenically unsaturated monomers for copolymerization withN-vinylcarboxamides further include carboxylic esters derived fromglycols or polyalkylene glycols where in each case only one OH group isesterified, for example hydroxyethyl acrylate, hydroxyethylmethacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate,hydroxypropyl methacrylate, hydroxybutyl methacrylate and alsomonoacrylate esters of polyalkylene glycols having a molar mass from 500to 10 000. Useful comonomers further include esters of ethylenicallyunsaturated carboxylic acids with amino alcohols such asdimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,diethylaminoethyl acrylate, diethylaminoethyl methacrylate,dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate,diethylaminopropyl acrylate, dimethylaminobutyl acrylate anddiethylaminobutyl acrylate. Basic acrylates can be used in the form ofthe free bases, the salts with mineral acids such as hydrochloric acid,sulfuric acid or nitric acid, the salts with organic acids such asformic acid, acetic acid, propionic acid or sulfonic acids or inquaternized form. Useful quaternizing agents include for exampledimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride orbenzyl chloride.

Useful comonomers further include amides of ethylenically unsaturatedcarboxylic acids such as acrylamide, methacrylamide and alsoN-alkylmonoamides and -diamides of monoethylenically unsaturatedcarboxylic acids with alkyl radicals of from 1 to 6 carbon atoms, forexample N-methylacrylamide, N,N-dimethylacrylamide,N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide andtert-butylacrylamide and also basic (meth)acrylamides, for exampledimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide,diethyl-aminoethylacrylamide, diethylaminoethylmethacrylamide,dimethylaminopropylacrylamide, diethylaminopropylacrylamide,dimethylaminopropylmethacrylamide and diethylaminopropylmethacrylamide.

Useful comonomers further include N-vinylpyrrolidone,N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazoleand also substituted N-vinylimidazoles such as, for exampleN-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole,N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole andN-vinylimidazolines such as N-vinylimidazoline,N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline.N-Vinylimidazoles and N-vinylimidazolines are used not only in the formof their free bases but also after neutralization with mineral acids ororganic acids or after quaternization, the quaternization beingpreferably effected with dimethyl sulfate, diethyl sulfate, methylchloride or benzyl chloride. Also useful are diallyldialkylammoniumhalides, for example diallyldimethylammonium chlorides.

Useful comonomers further include sulfo-containing monomers, for examplevinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid,styrenesulfonic acid, the alkali metal or ammonium salts of these acidsor 3-sulfopropyl acrylate, and the amphoteric copolymers contain morecationic units than anionic units, so that the polymers have a netcationic charge.

The copolymers contain for example

-   -   from 99.99 to 1 mol %, preferably from 99.9 to 5 mol %, of        N-vinylcarboxamides of the formula (I) and    -   from 0.01 to 99 mol %, preferably from 0.1 to 95 mol %, of other        monoethylenically unsaturated monomers copolymerizable therewith        in copolymerized form.

To prepare polymers containing vinylamine units, it is preferable tostart from homopolymers of N-vinylformamide or from copolymersobtainable by copolymerization of

-   -   N-vinylformamide with    -   vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile,        N-vinylcaprolactam, N-vinylurea, acrylic acid,        N-vinylpyrrolidone or C₁-C₆-alkyl vinyl ethers        and subsequent hydrolysis of the homo- or copolymers to form        vinylamine units from the copolymerized N-vinylformamide units,        the degree of hydrolysis being for example in the range from 0.1        to 100 mol %.

The hydrolysis of the hereinabove described polymers is effectedaccording to known lo processes by the action of acids, bases orenzymes. This converts the copolymerized monomers of the hereinaboveindicated formula (I) through detachment of the group

where R is as defined for the formula (I), into polymers which containvinylamine units of the formula (III)

where R¹ is as defined for the formula (I). When acids are used ashydrolyzing agents, the units (III) are present as ammonium salt.

The homopolymers of the N-vinylcarboxamides of the formula (1) and theircopolymers may be hydrolyzed to an extent in the range from 0.1 to 100mol %, preferably to an extent in the range from 70 to 100 mol %. Inmost cases, the degree of hydrolysis of the homo- and copolymers is inthe range from 5 to 95 mol %. The degree of hydrolysis of thehomopolymers is synonymous with the vinylamine units content of thepolymers. In the case of copolymers containing units derived from vinylesters, the hydrolysis of the N-vinylformamide units can be accompaniedby a hydrolysis of the ester groups with the formation of vinyl alcoholunits. This is the case especially when the hydrolysis of the copolymersis carried out in the presence of aqueous sodium hydroxide solution.Copolymerized acrylonitrile is likewise chemically modified in thehydrolysis, for example converted into amide groups or carboxyl groups.The homo- and copolymers containing vinylamine units may optionallycontain up to 20 mol % of amidine units, formed for example by reactionof formic acid with two adjacent amino groups or by intramolecularreaction of an amino group with an adjacent amide group, for example ofcopolymerized N-vinylformamide. The molar masses of the polymerscontaining vinylamine units range for example from 1 000 to 10 million,preferably from 10 000 to 5 million (determined by light scattering).This molar mass range corresponds for example to K values of from 5 to300, preferably from 10 to 250 (determined by the method of H.Fikentscher in 5% aqueous sodium chloride solution at 25° C. and apolymer concentration of 0.5% by weight).

The polymers containing vinylamine units are preferably used insalt-free form. Salt-free aqueous solutions of polymers containingvinylamine units are preparable for example from the hereinabovedescribed salt-containing polymer solutions by ultrafiltration usingsuitable membranes having molecular weight cutoffs at for example from 1000 to 500 000 dalton, preferably from 10 000 to 300 000 dalton. Thehereinbelow described aqueous solutions of other polymers containingamino and/or ammonium groups are likewise obtainable in salt-free formby ultrafiltration.

Useful cationic polymers further include polyethyleneimines.Polyethyleneimines are prepared for example by polymerizingethyleneimine in aqueous solution in the presence of acid-detachingcompounds, acids or Lewis acids. Polyethyleneimines have for examplemolar masses of up to 2 million, preferably from 200 to 500 000.Particular preference is given to using polyethyleneimines having molarmasses of from 500 to 100 000. Useful polyethyleneimines further includewater-soluble crosslinked polyethyleneimines which are obtainable byreaction of polyethyleneimines with crosslinkers such as epichlorohydrinor bischlorohydrin ethers of polyalkylene glycols containing from 2 to100 ethylene oxide and/or propylene oxide units. Also useful are amidicpolyethyleneimines which are obtainable for example by amidation ofpolyethyleneimines with C₁-C₂₂-monocarboxylic acids. Useful cationicpolymers further include alkylated polyethyleneimines and alkoxylatedpolyethyleneimines. Alkoxylation is carried out using for example from 1to 5 ethylene oxide or propylene oxide units per NH unit in thepolyethyleneimine.

Useful polymers containing amino and/or ammonium groups also includepolyamidoamines, which are preparable for example by condensingdicarboxylic acids with polyamines. Useful polyamidoamines are obtainedfor example when dicarboxylic acids having from 4 to 10 carbon atoms arereacted with polyalkylenepolyamines containing from 3 to 10 basicnitrogen atoms in the molecule. Useful dicarboxylic acids include forexample succinic acid, maleic acid, adipic acid, glutaric acid, subericacid, sebacic acid or terephthalic acid. Polyamidoamines may also beprepared using mixtures of dicarboxylic acids as well as mixtures ofplural polyalkylenepolyamines. Useful polyalkylenepolyamines include forexample diethylenetriamine, triethylenetetramine,tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine,dihexamethylenetriamine, aminopropylethylenediamine andbis-aminopropylethylenediamine. The dicarboxylic acids andpolyalkylenepolyamines are heated at an elevated temperature, forexample at from 120 to 220° C., preferably at from 130 to 180° C., toprepare the polyamidoamines. The water of condensation formed is removedfrom the system. The condensation may also employ lactones or lactams ofcarboxylic acids having from 4 to 8 carbon atoms. The amount of apolyalkylenepolyamine used per mole of a dicarboxylic acid is forexample in the range from 0.8 to 1.4 mol.

Amino-containing polymers further include ethyleneimine-graftedpolyamidoamines. They are obtainable from the hereinabove describedpolyamidoamines by reaction with ethyleneimine in the presence of acidsor Lewis acids such as sulfuric acid or boron trifluoride etherates atfor example from 80 to 100° C. Compounds of this kind are described forexample in DE-B-24 34 816.

Useful cationic polymers also include crosslinked or uncrosslinkedpolyamidoamines which may additionally have been grafted withethyleneimine prior to crosslinking. Crosslinked ethyleneimine-graftedpolyamidoamines are water soluble and have for example an average molarweight of from 3 000 to 1 million dalton. Customary crosslinkers includefor example epichlorohydrin or bischlorohydrin ethers of alkyleneglycols and polyalkylene glycols.

Further examples of cationic polymers that contain amino and/or ammoniumgroups are polydiallyldimethylammonium chlorides. Polymers of this kindare likewise known.

Useful cationic polymers further include copolymers of for example 1-99mol %, preferably 30-70 mol %, of acrylamide and/or methacrylamideand/or 1-vinylpyrrolidone and 99-1 mol %, preferably 70-30 mol %, ofcationic monomers such as dialkylaminoalkylacrylamide, dialkylaminoalkylacrylate, dialkylaminoalkylmethacrylamide and/or dialkylaminoalkylmethacrylate. The basic acrylamides and methacrylamides are preferablylikewise present in acid-neutralized form or in quaternized form.Examples are N-trimethylammoniumethylacrylamide chloride,N-trimethylammoniumethylmethacrylamide chloride,N-trimethylammoniumethyl methacrylate chloride, N-trimethylammoniumethylacrylate chloride, trimethylammoniumethylacrylamide methosulfate,trimethylammoniumethylmethacrylamide methosulfate,N-ethyldimethylammoniumethylacrylamide ethosulfate,N-ethyldimethylammoniumethylmethacrylamide ethosulfate,trimethylammoniumpropylacrylamide chloride,trimethylammoniumpropylmethacrylamide chloride,trimethylammoniumpropylacrylamide methosulfate,trimethylammoniumpropylmethacrylamide methosulfate andN-ethyldimethylammoniumpropylacrylamide ethosulfate.

Preference is given to trimethylammoniumpropylmethacrylamide chloride.

Further useful cationic monomers for preparing (meth)acrylamidecopolymers are diallyldimethylammonium halides and also basic(meth)acrylates. Useful examples are copolymers of 1-99 mol %,preferably 30-70 mol %, of acrylamide and/or methacrylamide and 99-1 mol%, preferably 70-30 mol %, of dialkylaminoalkyl acrylates and/ormethacrylates such as copolymers of acrylamide andN,N-dimethylaminoethyl acrylate or copolymers of acrylamide anddimethylaminopropyl acrylate. Basic acrylates or methacrylates arepreferably present in acid neutralized from or in quaternized form.Quaternization may be effected for example with methyl chloride or withdimethyl sulfate.

Useful cationic polymers containing amino and/or ammonium groups furtherinclude polyallylamines. Polymers of this kind are obtained byhomopolymerization of allylamine, preferably in acid neutralized form orin quaternized form, or by copolymerization of allylamine with othermonoethylenically unsaturated monomers described above as comonomers forN-vinylcarboxamides.

The cationic polymers have for example K values of from 8 to 300,preferably from 100 to 180 (determined by the method of H. Fikentscherin 5% aqueous sodium chloride solution at 25° C. and a polymerconcentration of 0.5% by weight). At pH 4.5, for example, they have acharge density of at least 1, preferably at least 4, meq/g ofpolyelectrolyte.

Examples of preferred cationic polymers are polydimethyldiallylammoniumchloride, polyethyleneimine, polymers containing vinylamine units,copolymers of acrylamide or methacrylamide that contain basic monomersin copolymerized form, polymers containing lysine units or mixturesthereof. Examples of preferred cationic polymers are:

-   -   copolymers of 50% of vinylpyrrolidone and 50% of        trimethylammoniumethyl methacrylate methosulfate, M_(w) 1        000-500 000;    -   copolymers of 30% of acrylamide and 70% of        trimethylammoniumethyl methacrylate methosulfate, M_(w) 1 000-1        000 000;    -   copolymers of 70% of acrylarnide and 30% of        dimethylaminoethylmethacrylamide, M_(w) 1 000-1 000 000;    -   copolymers of 50% of hydroxyethyl methacrylate and 50% of        2-dimethylarninoethylmethacrylamide, M_(w) 1 000-500 000;    -   polylysines of M_(w) 250-250 000, preferably 500-100 000, and        also lysine cocondensates having M_(w) molar masses from 250 to        250 000, the cocondensable component being selected for example        from amines, polyamines, ketene dimers, lactams, alcohols,        alkoxylated amines, alkoxylated alcohols and/or nonproteinogenic        amino acids,    -   vinylamine homopolymers, 1-99% of hydrolyzed        polyvinylformamides, copolymers of vinylformamide and vinyl        acetate, vinyl alcohol, vinylpyrrolidone or acrylamide having        molar masses of 3 000-500 000,    -   1-vinylimidazole homopolymers, 1-vinylimidazole copolymers with        1-vinylpyrrolidone, vinylformamide, acrylamide or vinyl acetate        having molar masses of from 5 000 to 500 000 and also their        quaternary derivatives, for example copolymer of 75% by weight        of 1-vinylimidazole and 25% by weight of 1-vinylpyrrolidone        having M_(w)=50 000, copolymer of 50% by weight of        3-methyl-1-vinylimidazolium chloride and 50% by weight of        1-vinylpyrrolidone having M_(w)=75 000,    -   polyethyleneimines, crosslinked polyethyleneimines or amidated        polyethyleneimines having molar masses of from 500 to 3 000 000,        for example polyethyleneimine of molar mass 25 000 or high        molecular weight polyethyleneimine of molar mass 2 000 000,    -   amine-epichlorohydrin polycondensates which contain imidazole,        piperazine, C₁-C₈-alkylamines, C₁-C₈-dialkylamines and/or        dimethylaminopropylamine as amine component and have a molar        mass of from 500 to 250 000,    -   polydimethyldiallylammonium chloride, M_(w) 2 000-2 000 000, and    -   polymers containing basic (meth)acrylamide or (meth)acrylic        ester units, polymers containing basic quaternary        (meth)acrylamide or (meth)acrylic ester units having molar        masses of from 10 000 to 2 000 000.

Particular preference is given to polyethyleneimines, crosslinkedpolyethyleneimines, amidated polyethyleneimines, amine-epichlorohydrinpolycondensates with imidazole or piperazine as amine component,polydimethyldiallylammonium chlorides and also polyvinylformamideshaving a degree of hydrolysis of from 30 to 100%.

It is also possible to include a minor amount (<10% by weight) ofanionic comonomers, for example acrylic acid, methacrylic acid,vinylsulfonic acid or alkali metal salts of the acids mentioned.

C Compositions for Treating Surfaces

There are many industrial and domestic applications where themodification of the properties of textile and nontextile surfaces withpolymer dispersions is important. It is not always possible to effectthe modification of the surfaces by impregnating, spraying and spreadingoperations involving concentrated dispersions. It is frequentlydesirable to effect the modification of the surface by rinsing thesurface with a very dilute liquor that contains an active substance. Itis frequently desirable to combine the modifying treatment of thesurface with a wash, clean and/or conditioning or impregnation of thesurface. Surfaces contemplated include in particular surfaces of textilematerials such as cotton fabrics and cotton blend fabrics, but also hardsurfaces.

The present invention also provides a process for modifying the surfaceof textile and nontextile materials, which comprises cationicallymodified particulate polyurethanes having a particle size from 10 nm to100 μm being applied to said surface of said materials from an aqueousdispersion and said materials being dried.

Preferably, the cationically modified particulate polyurethanes areapplied to the surface from an aqueous dispersion having a polyurethanecontent of ≦5% by weight.

The surfaces of textile materials may be modified for example to providethem with water resistance, a soil release finish, a soil resist finish,improved integrity of the fiber ensemble, hand improvement, protectionagainst wrinkling and creasing and protection against chemical ormechanical effects and damage.

Surfaces contemplated here are in particular surfaces of textilematerials such as cotton fabrics and cotton blend fabrics. In addition,installed carpeting and furniture covers can be treated according to thepresent invention.

The surfaces of nontextile materials may be modified for example toprovide them with water resistance, a soil release finish, a soil resistfinish and protection against chemical or mechanical effects and damage.

Surfaces of nontextile materials include for example the macroscopic,hard surfaces of floor and wall coverings, exposed concrete, brickexteriors, rendered exteriors, glass, ceramic, metal, enamel, plasticand wood and also the microscopic surfaces of porous bodies, foams,woods, of leather, porous building materials and pulp fleeces.

The cationically modified particulate anionic polyurethanes are used formodifying surfaces of the hereinabove exemplified materials as asurface-modifying ingredient in rinsing or conditioning compositions,washing or cleaning compositions for textile and nontextile materials.Especially contemplated are uses in washing, cleaning and aftertreatingof textiles, leather, wood, floor coverings, glass, ceramics and othersurfaces in the home and in the industrial sector.

The cationically modified particulate anionic polyurethanes are used inthe form of a dilute, predominantly aqueous, dispersion. The use takesthe form of a treatment of the surfaces with washing, cleaning andrinsing liquors to which the polymers are added either directly or bymeans of a liquid or solid formulation, or in the form of a finelydivided application of a liquid formulation, for example by spraying.

The cationically modified particulate anionic polyurethanes can be usedfor example as sole active component in aqueous rinsing and conditioningcompositions and, depending on the composition of the polyurethane,provide for easier soil release in a subsequent wash, reduced soilattachment in the use of the textiles, improved structural integrity offibers, improved shape retention and structural integrity for fabrics,water repellency on the surface of the washed material and also handimprovement.

The concentration of the cationically modified particulate polyurethaneswhen used in a rinsing or conditioning bath, a washing liquor orcleaning bath is for example in the range from 0.0002 to 5% by weight,preferably in the range from 0.0005 to 1.0% by weight and morepreferably in the range from 0.002 to 0.1% by weight.

The cationic modification of the particulate polyurethanes is preferablyeffected prior to use in the aqueous treatment compositions, but canalso be effected in the course of the production of the aqueoustreatment compositions, by mixing aqueous dispersions of the particulatepolyurethanes with the other ingredients of the treatment composition inthe presence of cationic polymers and optionally cationic surfactants.The particulate polyurethanes or formulations containing them can alsobe added directly to the rinsing, washing or cleaning liquor providedthe liquor contains adequate amounts of cationic polymers in dissolvedform.

Compositions for treating surfaces can have the following compositionfor example:

-   -   (a) from 0.1 to 50% by weight, preferably from 0.5 to 25% by        weight, of the cationically modified particulate anionic        polyurethanes,    -   (b) from 0 to 60% by weight of at least one customary additive        such as acids or bases, inorganic builders, organic cobuilders,        surfactants, polymeric dye transfer inhibitors, polymeric soil        antiredeposition agents, soil release polymers, enzymes,        complexing agents, corrosion inhibitors, waxes, silicone oils,        light stabilizers, dyes, solvents, hydrotropes, thickeners        and/or alkanolamines,    -   (c) from 0 to 99.9% by weight of water,        components (a) to (c) adding up to 100% by weight.

The present invention also provides a textile treatment compositionincluding

-   -   a) from 0.1 to 40% by weight, preferably from 0.5 to 25% by        weight, of the cationically modified particulate anionic        polyurethanes,    -   b) from 0 to 30% by weight of silicones,    -   c) from 0 to 30% by weight of cationic and/or nonionic        surfactants,    -   d) from 0 to 60% by weight of further ingredients such as        further wetting agents, softeners, lubricants, water-soluble,        film-forming and adhesive polymers, scents, dyes, stabilizers,        fiber and color protection additives, viscosity modifiers, soil        release additives, corrosion control additives, bactericides,        preservatives and spraying assistants, and    -   e) from 0 to 99.9% by weight of water,        components a) to e) adding up to 100% by weight.

Preferred silicones b) are amino-containing silicones, which arepreferably present in microemulsified form, alkoxylated, especiallyethoxylated, silicones, polyalkylene oxide-polysiloxanes, polyalkyleneoxide-aminopolydimethylsiloxanes, silicones having quaternary ammoniumgroups (silicone quats) and silicone surfactants.

Useful softeners or lubricants include for example oxidizedpolyethylenes or paraffinic waxes and oils. Useful water-soluble,film-forming and adhesive polymers include for example (co)polymersbased on acrylamide, N-vinylpyrrolidone, vinylformamide,N-vinylimidazole, vinylamine, N,N′-dialkylaminoalkyl (meth)acrylates,N,N′-dialkylaminoalkyl, (meth)acrylamides, (meth)acrylic acid, alkyl(meth)acrylates and/or vinylsulfonate. The aforementioned basic monomersmay also be used in quaternized form.

A textile treatment composition to be applied to the textile material byspraying may additionally include a spraying assistant. In some cases,it may also be preferable to include alcohols such as ethanol,isopropanol, ethylene glycol or propylene glycol in the formulation.Further customary additives are scents, dyes, stabilizers, fiber andcolor protection additives, viscosity modifiers, soil release additives,corrosion control additives, bactericides and preservatives in thecustomary amounts.

The textile treatment composition may generally also be applied byspraying in the course of ironing after laundering. This not onlysubstantially facilitates the ironing, but also imparts sustainedwrinkle and crease resistance to the textiles.

The cationically modified particulate inorganic polyurethanes can alsobe used in the main wash cycle of a washing machine used for washingtextiles.

The present invention further provides a solid laundry detergentformulation including

-   -   a) from 0.05 to 20% by weight of the cationically modified        particulate anionic polyurethanes,    -   b) from 0 to 20% by weight of silicones,    -   c) from 0.1 to 40% by weight of nonionic and/or anionic        surfactants,    -   d) from 0 to 50% by weight of inorganic builders,    -   e) from 0 to 10% by weight of organic cobuilders,    -   f) from 0 to 60% by weight of other customary ingredients such        as extenders, enzymes, perfume, complexing agents, corrosion        inhibitors, bleaches, bleach activators, bleach catalysts,        cationic surfactants, dye transfer inhibitors, soil        antiredeposition agents, soil release polyesters, dyes,        bactericides, dissolution improvers and/or disintegrants,        components a) to f) adding up to 100% by weight.

A solid laundry detergent formulation according to the present inventionis customarily pulverulent or granular or in extrudate-or tablet form.

The present invention further provides a liquid laundry detergentformulation including

-   -   a) from 0.05 to 20% by weight of the cationically modified        particulate anionic polyurethanes,    -   b) from 0 to 20% by weight of silicones,    -   c) from 0.1 to 40% by weight of nonionic and/or anionic        surfactants,    -   d) from 0 to 20% by weight of inorganic builders,    -   e) from 0 to 10% by weight of organic cobuilders,    -   f) from 0 to 60% by weight of other customary ingredients such        as sodium carbonate, enzymes, perfume, complexing agents,        corrosion inhibitors, bleaches, bleach activators, bleach        catalysts, cationic surfactants, dye transfer inhibitors, soil        antiredeposition agents, soil release polyesters, dyes,        bactericides, nonaqueous solvents, solubilizers, hydrotropes,        thickeners and/or alkalolamines,    -   g) from 0 to 99.85% by weight of water,        components a) to g) adding up to 100% by weight.

Useful silicones b) include the abovementioned silicones.

Useful anionic surfactants c) include in particular:

-   -   (fatty) alcohol sulfates of (fatty) alcohols having from 8 to        22, preferably from 10 to 18, carbon atoms, for example C₉- to        C₁₁-alcohol sulfates, C₁₂- to C₁₄-alcohol sulfates, C₁₂- to        C₁₈-alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl        sulfate, palmityl sulfate, stearyl sulfate and tallow fatty        alcohol sulfate;    -   sulfated alkoxylated C₈- to C₂₂-alcohols (alkyl ether sulfates).        Compounds of this kind are prepared for example by first        alkoxylating a C₈- to C₂₂-alcohol, preferably a C₁₀- to        C₁₈-alcohol, for example a fatty alcohol, and then sulfating the        alkoxylation product. The alkoxylation is preferably carried out        using ethylene oxide;    -   linear or branched C₈- to C₂₀-alkylbenzenesulfonates (LAS),        preferably linear C₉- to C₁₃-alkylbenzenesulfonates and        -alkyltoluenesulfonates;    -   alkanesulfonates such as C₈- to C₂₄-alkanesulfonates, preferably        C₁₀- to C₁₈-alkanesulfonates;    -   soaps such as, for example, the sodium and potassium salts of        C₈- to C₂₄-carboxylic acids.

The anionic surfactants mentioned are preferably included in the laundrydetergent in the form of salts. Suitable cations in these salts arealkali metal ions such as sodium, potassium and lithium ions andammonium ions such as hydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium.

Useful nonionic surfactants c) are in particular:

-   -   alkoxylated linear or branched C₈- to C₂₂-alcohols such as fatty        alcohol alkoxylates or oxo alcohol alkoxylates. These may have        been alkoxylated with ethylene oxide, propylene oxide and/or        butylene oxide. Useful surfactants here include all alkoxylated        alcohols which contain at least two molecules of one of the        aforementioned alkylene oxides. Here it is possible to use block        polymers of ethylene oxide, propylene oxide and/or butylene        oxide or addition products which contain the aforementioned        alkylene oxides in random distribution. Nonionic surfactants        generally contain from 2 to 50, preferably from 3 to 20, mol of        at least one alkylene oxide per mole of alcohol. The alkylene        oxide component is preferably ethylene oxide. The alcohols        preferably have from 10 to 18 carbon atoms. Depending on the        type of alkoxylation catalyst used to make them, alkoxylates        have a broad or narrow alkylene oxide homolog distribution;    -   alkylphenol alkoxylates such as alkylphenol ethoxylates having        C₆-C₁₄-alkyl chains and from 5 to 30 alkylene oxide units;    -   alkylpolyglucosides having from 8 to 22, preferably from 10 to        18, carbon atoms in the alkyl chain and generally from 1 to 20,        preferably from 1.1 to 5, glucoside units;    -   N-alkylglucamides, fatty acid amide alkoxylates, fatty acid        alkanolamide alkoxylates and also block copolymers of ethylene        oxide, propylene oxide and/or butylene oxide.

Useful inorganic builders d) are in particular:

-   -   crystalline or amorphous aluminosilicates having ion-exchanging        properties such as zeolites in particular. Useful zeolites        include in particular zeolites A, X, B, P, MAP and HS in their        sodium form or in forms in which sodium has been partly replaced        by other cations such as lithium, potassium, calcium, magnesium        or ammonium;    -   crystalline silicates such as in particular disilicates or        sheet-silicates, for example δ-Na₂Si₂O₅ or P—Na₂Si₂O₅. Silicates        can be used in the form of their alkali metal, alkaline earth        metal or ammonium salts, preferably as sodium, lithium and        magnesium silicates;    -   amorphous silicates such as for example sodium metasilicate or        amorphous disilicate;    -   carbonates and bicarbonates. These can be used in the form of        their alkali metal, alkaline earth metal or ammonium salts.        Preference is given to sodium, lithium and magnesium carbonates        or bicarbonates, especially sodium carbonate and/or sodium        bicarbonate;    -   polyphosphates such as for example pentasodium triphosphate.

Useful organic cobuilders e) include in particular low molecular weight,oligomeric or polymeric carboxylic acids.

-   -   Useful low molecular weight carboxylic acids include for example        citric acid, hydrophobic modified citric acid such as for        example agaric acid, malic acid, tartaric acid, gluconic acid,        glutaric acid, succinic acid, imidodisuccinic acid,        oxydisuccinic acid, propanetricarboxylic acid,        butanetetracarboxylic acid, cyclopentanetetracarboxylic acid,        alkyl- and alkenylsuccinic acids and aminopolycarboxylic acids        such as for example nitrilotriacetic acid, β-alaninediacetic        acid, ethylenediaminetetraacetic acid, serinediacetic acid,        isoserinediacetic acid, N-(2-hydroxyethyl)iminodiacetic acid,        ethylenediaminedisuccinic acid and methyl- and        ethylglycinediacetic acid;    -   useful oligomeric or polymeric carboxylic acids include for        example homopolymers of acrylic acid, oligomaleic acids,        copolymers of maleic acid with acrylic acid, methacrylic acid,        C₂-C₂₂-olefins such as for example isobutene or long-chain        α-olefins, vinyl alkyl ethers having C₁-C₈-alkyl groups, vinyl        acetate, vinyl propionate, (meth)acrylic esters of        C₁-C₈-alcohols and styrene. Preference is given to using the        homopolymers of acrylic acid and copolymers of acrylic acid with        maleic acid. Polyaspartic acids are also useful as organic        cobuilders. Oligomeric and polymeric carboxylic acids are used        in acid form or as sodium salt.

Useful bleaches include for example adducts of hydrogen peroxide withinorganic salts such as for example sodium perborate monohydrate, sodiumperborate tetrahydrate or sodium carbonate perhydrate or percarboxylicacids such as for example phthalimidopercaproic acid.

Useful bleach activators include for exampleN,N,N′,N′-tetraacetylethylenediamine (TAED), sodiump-nonanoyloxybenzenesulfonate or N-methylmorpholinium acetonitrilemethosulfate.

Preferred enzymes for use in laundry detergents are proteases, lipases,amylases, cellulases, oxidases or peroxidases.

Useful dye transfer inhibitors include for example homo- and copolymersof 1-vinylpyrrolidone, of 1-vinylimidazole or of 4-vinylpyridineN-oxide. Homo- or copolymers of 4-vinylpyridine which have been reactedwith chloroacetic acid are likewise useful as dye transfer inhibitors.

A detailed description of the laundry detergent ingredients mentionedmay be found for example in WO 99/06524 or WO 99/04313 and in LiquidDetergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, MarcelDecker, New York, 1997, p. 272-304. For typical ingredients also see theDetergents chapter (part 3, Detergent Ingredients, part 4, HouseholdDetergents and part 5, Institutional Detergents) in Ullmann'sEncyclopedia of Industrial Chemistry, Sixth Edition, 2000 ElectronicVersion 2.0.

The concentration of the cationically modified particulate anionicpolyurethanes in the washing liquor is for example in the range from 10to 5 000 ppm and preferably in the range from 50 to 1 000 ppm. Thetextiles treated with the cationically modified particulatepolyurethanes in the main wash cycle of a washing machine not onlywrinkle substantially less than untreated textiles, they are also easierto iron, softer and smoother, more dimensionally and shape stable and,because of the fiber and color protection, look less used, ie exhibitless fluff and fewer knots and less color damage or fading, afterrepeated washing.

The cationically modified particulate anionic polyurethanes can also beused in the rinse or conditioning cycle following the main wash cycle.The concentration of the particulate polyurethanes in the washing liquoris for example in the range from 10 to 5 000 ppm and is preferably inthe range from 50 to 1 000 ppm. The ingredients typical of a fabricconditioner can be included in the rinsing liquor, if desired. Textilestreated in this way and then dried on the line or preferably in a tumbledryer likewise exhibit a very high level of crease control associatedwith the above-described positive outworkings on the ironing. Creasecontrol can be substantially enhanced by briefly ironing the textilesonce after drying. The treatment in the conditioning or rinse cycle alsohas a favorable effect on the shape retention of the textiles. Itfurther inhibits the formation of knots and fluff and suppresses colordamage.

The present invention further provides a laundry rinse conditionerincluding

-   -   a) from 0.05% to 40% by weight of the cationically modified        particulate anionic polyurethanes,    -   b) from 0 to 20% by weight of silicones,    -   c) from 0.1 to 40% by weight of cationic surfactants,    -   d) from 0 to 30% by weight of nonionic surfactants,    -   e) from 0 to 30% by weight of other customary ingredients such        as lubricants, wetting agents, film-forming polymers, scents,        dyes, stabilizers, fiber and color protection additives,        viscosity modifiers, soil release additives, corrosion control        additives, bactericides and preservatives, and    -   f) from 0 to 99.85% by weight of water,        components a) to f) adding up to 100% by weight.

Useful silicones b) include the abovementioned silicones.

Preferred cationic surfactants c) are selected from the group of thequaternary diesterammonium salts, the quaternary tetraalkylammoniumsalts, the quaternary diamidoammonium salts, the amidoamine esters andimidazolium salts. These are preferably present in an amount of from 3to 30% by weight in the laundry refreshers. Examples are quaternarydiesterammonium salts which have two C₁₁- toC₂₂-alk(en)ylcarbonyloxy(mono- to pentamethylene) radicals and two C₁-to C₃-alkyl or -hydroxyalkyl radicals on the quaternary nitrogen atomand, for example, chloride, bromide, methosulfate or sulfate ascounterion.

Quaternary diesterammonium salts further include in particular thosewhich have a C₁₁- to C₂₂-alk(en)ylcarbonyloxytrimethylene radicalbearing a C₁₁- to C₂₂-alk(en)ylcarbonyloxy radical on the central carbonatom of the trimethylene group and three C₁- to C₃-alkyl or-hydroxyalkyl radicals on the quaternary nitrogen atom and, for example,chloride, bromide, methosulfate or sulfate as counterion.

Quaternary tetraalkylammonium salts are in particular those which havetwo C₁- to C₆-alkyl radicals and two C₈- to C₂₄-alk(en)yl radicals onthe quaternary nitrogen atom and, for example, chloride, bromide,methosulfate or sulfate as counterion.

Quaternary diamidoammonium salts are in particular those which bear twoC₈- to C₂₄-alk(en)ylcarbonylaminoethylene radicals, a substituentselected from hydrogen, methyl, ethyl and polyoxyethylene having up to 5oxyethylene units and as fourth radical a methyl group on the quaternarynitrogen atom and, for example, chloride, bromide, methosulfate orsulfate as counterion.

Amidoamino esters are in particular tertiary amines bearing a C₁₁- toC₂₂-alk(en)ylcarbonylamino(mono- to trimethylene) radical, a C₁₁- toC₂₂-alk(en)ylcarbonyloxy(mono- to trimethylene) radical and a methylgroup as substituents on the nitrogen atom.

Imidazolinium salts are in particular those which bear a C₁₄- toC₁₈-alk(en)yl radical in position 2 of the heterocycle, a C₁₄- toC₁₈-alk(en)ylcarbonyl(oxy or amino)ethylene radical on the neutralnitrogen atom and hydrogen, methyl or ethyl on the nitrogen atomcarrying the positive charge, while counterions here are for examplechloride, bromide, methosulfate or sulfate.

The examples hereinbelow illustrate the invention.

EXAMPLES

Preparation of Anionic Dispersions I and II

Example 1

Dispersion I

400 g (0.200 mol) of a polyesterpolyol formed from adipic acid,neopentylglycol and hexanediol and having an OH number of 56 wereinitially charged to a stirred tank at 50° C. 36.1 g (0.1624 mol) ofisophorone diisocyanate, 42.9 g (0.1624 mol) ofbis-(4-isocyanatocyclohexyl)methane and 80 g of acetone were added. Themixture was stirred at 90° C. for 60 min before 0.15 g of dibutyltindilaurate was added. Stirring was continued for a further 120 min. Themixture was then diluted with 500 g of acetone and at the same timecooled to 50° C. The NCO content of the solution was 0.99% (reckoned0.94%). The addition of 22.5 g (0.0534 mol) of a 50% by weight aqueoussolution of the sodium salt of aminoethyl aminoethane sulfonic acid wasfollowed by dispersion in the course of 5 min by addition of 800 g ofwater. After dispersion, a solution of 3.9 g (0.0379 mol) ofdiethylenetriamine and 1.8 g (0.0106 mol) of isophoronediamine in 50 gof water was added. The acetone was removed by distillation to leave afinely divided aqueous anionic PU dispersion having a solids content ofabout 40%.

Example 2

Dispersion II

400 parts of a propylene glycol having an OH number of 56 were dewateredin a stirred flask at 130° C. and 20 Torr for 30 minutes. The polyetherwas cooled down, dissolved in 50 parts of N-methylpyrrolidone andadmixed with 26.8 parts of dimethylolpropionic acid. This was followedby stirring with 95.7 parts of tolylene diisocyanate (isomer ratio2.4/2.6=80/20) at 110° C. for 120 minutes. This was followed by dilutionwith 400 parts of acetone and cooling to 50° C. 16 parts oftriethylamine were added dropwise to the solution thus obtained,followed 10 minutes later by 900 parts of water, added dropwise, beforethe acetone was distilled off under reduced pressure to leave a veryfinely divided stable anionic dispersion having a solids content of 40%.

Preparation of Cationically Modified Dispersions III, IV and V

The following cationic polymers were used:

-   -   Polymer 1: polyethyleneimine having a molar mass of 25 000    -   Polymer 2: high molecular weight polyethyleneimine having a        molar mass of 2 000 000    -   Polymer 3: polydiallyldimethylammonium chloride having a molar        mass of 100 000.

Example 3

Dispersion III

50 g of dispersion I were metered into 50 g of a 0.8% by weight aqueoussolution of polymer 1 at room temperature and pH 7 in the course of 10minutes. The finely divided dispersion obtained was stable for severalmonths.

Example 4

Dispersion IV

50 g of dispersion I were metered into 100 g of a 0.8% by weight aqueoussolution of polymer 2 at room temperature and pH 7 in the course of 10minutes. The finely divided dispersion obtained was stable for severalmonths.

Example 5

Dispersion V

50 g of dispersion II were metered into 50 g of a 1.2% by weight aqueoussolution of polymer 3 at room temperature and pH 7 in the course of 10minutes. The finely divided dispersion obtained was stable for severalmonths.

Electrophoretic measurements demonstrated the coating of the anionic PUparticles with the cationic polymer. The coating caused the direction ofmigration of the particles in an electric field to reverse.

Measurement of Dry Crease Recovery Angle

Inventive Examples 6 to 8 and Comparative Examples 1 to 3

Dispersion III was diluted with water (pH 7, water hardness 1 mmol/l) toa solids content of 0.02% by weight. A white cotton fabric (10 g) wassuspended in the stirred liquor (600 ml) for 30 minutes. The cottonfabric was then removed and dried. Crease recovery (dewrinkling) wasdetermined on the dry fabric in accordance with DIN 53890. The higherthe crease recovery angle after removal of the force acting on thefabric, the better the efficacy of the dispersion. A white cotton fabricwas similarly treated with dispersions IV and V and, for comparison,with the unmodified dispersions I and II before the crease recoveryangle was determined in similar fashion. The results are reported inTable 1 TABLE 1 Crease recovery angle Example Cotton fabric treated withTotal (warp + fill) Comparative 1 Dispersion I 70 Comparative 2Dispersion II 60 Inventive 6 Dispersion III 95 Inventive 7 Dispersion IV105 Inventive 8 Dispersion V 80 Comparative 3 untreated 50

The results demonstrate the superior efficacy of the cationicallymodified polyurethane dispersions II, IV and V over the unmodifiedanionic polyurethane dispersions I and II.

Application of Dispersions in Rinse Cycle

Inventive Examples 9 to 12 and Comparative Examples 4 to 6

White sheetlike cotton fabric 30 cm×50 cm in size and having a basisweight of 130 g/m² was washed in the presence of ballast fabric (load:1.5 kg) at a water hardness of 3 mmol/l. The washing operation was madeup of a main wash cycle (Ariel® hydractive laundry detergent, 40° C.coloreds program) and a subsequent rinse cycle. The rinse liquorcontained

-   -   a) 1000 ppm of a commercially available fabric conditioner        (Downy from Lenor®)    -   b) 1000 ppm of Downy from Lenor+100 ppm of dispersion I, III or        IV (active material)    -   c) 200 ppm of dispersion I, III or IV (active material)

The liquor ratio was 10:1. After the rinse cycle, the fabric was removedand dried in a tumble dryer (cupboard dry program). After drying, thesheetlike fabric samples were visually rated on the lines of AATCC testmethod 124, where a rating of 1 denotes that the fabric is very wrinklyand has many creases, while a rating of 5 is awarded to wrinkle- andcrease-free fabric.

The results are reported in Table 2. TABLE 2 Example Rinse cycle Co (30cm × 50 cm) Comparative 4 1000 ppm Downy 1.5 Comparative 5 1000 ppmDowny + 100 ppm 2.0 Dispersion I  9 1000 ppm Downy + 100 ppm 2.5Dispersion III 10 1000 ppm Downy + 100 ppm 3.0 Dispersion IV Comparative6 200 ppm Dispersion I 2.0 11 200 ppm Dispersion III 2.5 12 200 ppmDispersion IV 3.0

The results show that the cationically modified Dispersions III and IVare distinctly superior to anionic Dispersion I.

1-13. (canceled)
 14. Cationically modified particulate anionicpolyurethanes having a particle size from 10 nm to 10 μm, theparticulate polyurethanes being cationically modified through surfacecoating with cationic polymers.
 15. The cationically modifiedparticulate anionic polyurethanes as claimed in claim 14, wherein saidparticulate polyurethanes contain anionic and cationic and/or nonionichydrophilic groups.
 16. The cationically modified particulate anionicpolyurethanes as claimed in claim 14, wherein said cationic polymersused, are selected from polymers containing vinylamine units, polymerscontaining vinylimidazole units, polymers containing quaternaryvinylimidazole units, condensates of imidazole and epichlorohydrin,crosslinked polyamidoamines, ethyleneimine-grafted crosslinkedpolyamidoamines, polyethyleneimines, alkoxylated polyethyleneimines,crosslinked polyethyleneimines, amidated polyethyleneimines, alkylatedpolyethyleneimines, polyamines, amine-epichlorohydrin polycondensates,alkoxylated polyamines, polyallylamines, polydimethyldiallylammoniumchlorides, polymers containing basic (meth)acrylamide or (meth)acrylicester units, polymers containing basic quaternary (meth)acrylamide or(meth)acrylic ester units, lysine condensates or combinations thereof.17. Cationically modified aqueous anionic polyurethane dispersions,comprising cationically modified particulate anionic polyurethanes asclaimed in claim
 14. 18. A process for modifying the surface of textileand nontextile materials, comprising applying cationically modifiedparticulate anionic polyurethanes, as claimed in claim 14, to saidsurface of said materials, from an aqueous dispersion and drying saidmaterials.
 19. The process as claimed in claim 18, wherein saidpolyurethanes are applied to said surface from an aqueous dispersionhaving a polyurethane content of <5% by weight.
 20. A compositioncomprising the cationically modified particulate anionic polyurethanesas claimed in claim 14, as a surface-modifying additive, and one or moreadditives used in washing, rinsing, conditioning or cleaningcompositions.
 21. A composition comprising the cationically modifiedaqueous anionic polyurethane dispersions as claimed in claim 17, and oneor more additives used in washing, rinsing or cleaning liquors.
 22. Acomposition for treating surfaces, comprising (a) from 0.1 to 50% byweight of cationically modified particulate anionic polyurethanes asclaimed in claim 14, (b) from 0 to 60% by weight of at least onecustomary additive, such as acids or bases, inorganic builders, organiccobuilders, surfactants, polymeric dye transfer inhibitors, polymericsoil antiredeposition agents, soil release polymers, enzymes, complexingagents, corrosion inhibitors, waxes, silicone oils, light stabilizers,dyes, solvents, hydrotropes, thickeners and/or alkanolamines, (c) from 0to 99.9% by weight of water, wherein components (a) to (c) add up to100% by weight.
 23. A textile treatment composition, comprising a) from0.1 to 40% by weight of the cationically modified particulate anionicpolyurethanes of claim 14, b) from 0 to 30% by weight of silicones, c)from 0 to 30% by weight of cationic and/or nonionic surfactants, d) from0 to 60% by weight of further ingredients, such as further wettingagents, softeners, lubricants, water-soluble, film-forming and adhesivepolymers, scents, dyes, stabilizers, fiber and color protectionadditives, viscosity modifiers, soil release additives, corrosioncontrol additives, bactericides, preservatives and spraying assistants,and e) from 0 to 99.9% by weight of water, wherein components a) to e)add up to 100% by weight.
 24. A solid laundry detergent formulation,comprising a) from 0.05 to 20% by weight of the cationically modifiedparticulate anionic polyurethanes of claim 14, b) from 0 to 20% byweight of silicones, c) from 0.1 to 40% by weight of nonionic and/oranionic surfactants, d) from 0 to 50% by weight of inorganic builders,e) from 0 to 10% by weight of organic cobuilders, f) from 0 to 60% byweight of other customary ingredients, such as extenders, enzymes,perfume, complexing agents, corrosion inhibitors, bleaches, bleachactivators, cationic surfactants, bleach catalysts, dye transferinhibitors, soil antiredeposition agents, soil release polyesters, dyes,bactericides, dissolution improvers and/or disintegrants, whereincomponents a) to f) add up to 100% by weight.
 25. A liquid laundrydetergent formulation, comprising a) from 0.05 to 20% by weight of thecationically modified particulate anionic polyurethanes of claim 14, b)from 0 to 20% by weight of silicones, c) from 0.1 to 40% by weight ofnonionic and/or anionic surfactants, d) from 0 to 20% by weight ofinorganic builders, e) from 0 to 10% by weight of organic cobuilders, f)from 0 to 60% by weight of other customary ingredients, such as sodiumcarbonate, enzymes, perfume, complexing agents, corrosion inhibitors,bleaches, bleach activators, bleach catalysts, cationic surfactants, dyetransfer inhibitors, soil antiredeposition agents, soil releasepolyesters, dyes, bactericides, nonaqueous solvents, solubilizers,hydrotropes, thickeners and/or alkanolamines, g) from 0 to 99.85% byweight of water, wherein components a) to g) add up to 100% by weight.26. A laundry rinse conditioner, comprising a) from 0.05% to 40% byweight of the cationically modified particulate anionic polyurethanes ofclaim 14, b) from 0 to 20% by weight of silicones, c) from 0.1 to 40% byweight of cationic surfactants, d) from 0 to 30% by weight of nonionicsurfactants, e) from 0 to 30% by weight of other customary ingredients,such as silicones, other lubricants, wetting agents, film-formingpolymers, scents, dyes, stabilizers, fiber and color protectionadditives, viscosity modifiers, soil release additives, corrosioncontrol additives, bactericides and preservatives, and f) from 0 to99.85% by weight of water, wherein components a) to f) add up to 100% byweight.